SpringerLink
Log in

Activation of C2H6, C3H8, HC(CH3)3, and c-C3H6 by gas-phase Ru+ and the thermochemistry of Ru-ligand complexes

  • Published:
Journal of the American Society for Mass Spectrometry

Abstract

The reactions of Ru+ with C2H6, C3H8, HC(CH3)3, and c-C3H6 at hyperthermal energies have been studied using guided ion beam mass spectrometry. It is found that dehydrogenation is efficient and the dominant process at low energies in all four reaction systems. At high energies, C-H cleavage processes dominate the product spectrum for the reactions of Ru+ with ethane, propane, and isobutane. C-C bond cleavage is a dominant process in the cyclopropane system. The reactions of Ru+ are compared with those of the first-row transition metal congener Fe+ and the differences in behavior and mechanism are discussed in some detail. Modeling of the endothermic reaction cross sections yields the 0-K bond dissociation energies (in eV) of D 0(Ru-H)=2.27±0.15, D 0(Ru+-C)=4.70±0.11, D 0(Ru+-CH)=5.20±0.12, D 0(Ru+-CH2)=3.57±0.05, D 0(Ru+-CH3)=1.66±0.06, D 0(Ru-CH3)=1.68±0.12, D 0(Ru+-C2H2)=1.98±0.18, D 0(Ru+-C2H3)=3.03±0.07, and D 0(Ru+-C3H4)=2.24±0.12. Speculative bond energies for Ru+=CCH2 of 3.39±0.19 eV and Ru+=CHCH3 of 3.19±0.15 eV are also obtained. The observation of exothermic processes sets lower limits for the bond energies of Ru+ to ethene, propene, and isobutene of 1.34, 1.22, and 1.14 eV, respectively.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Subscribe and save

Springer+ Basic
EUR 32.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or Ebook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Allison, J. Prog. Inorg. Chem. 1986, 34, 627.

    Article  CAS  Google Scholar 

  2. Squires, R. R. Chem. Rev. 1987, 87, 623.

    Article  CAS  Google Scholar 

  3. Gas Phase Inorganic Chemistry; Russell, D. H., Ed.; Plenum: New York, 1989.

    Google Scholar 

  4. Eller, K.; Schwarz, H. Chem. Rev. 1991, 91, 1121.

    Article  CAS  Google Scholar 

  5. For reviews, see Armentrout, P. B. In Selective Hydrocarbon Activation: Principles and Progress; Davies, J. A.; Watson, P. L.; Greenberg, A.; Liebman, J. F., Eds.; VCH: New York, 1990; p 467.

    Google Scholar 

  6. Armentrout, P. B. In Gas Phase Inorganic Chemistry; Russell, D. H., Ed.; Plenum: New York, 1989; p 1.

    Google Scholar 

  7. Armentrout, P. B.; Beauchamp, J. L. Acc. Chem. Res. 1989, 22, 315.

    Article  CAS  Google Scholar 

  8. For reviews, see Armentrout, P. B. Science 1991, 251, 175.

    Article  CAS  Google Scholar 

  9. Armentrout, P. B. Annu. Rev. Phys. Chem. 1990, 41, 313.

    Article  CAS  Google Scholar 

  10. Weisshaar, J. C. Adv. Chem. Phys. 1992, 82, 213.

    Article  CAS  Google Scholar 

  11. Weisshaar, J. C. Acc. Chem. Res. 1993, 26, 213.

    Article  CAS  Google Scholar 

  12. van Koppen, P. A. M.; Kemper, P. R.; Bowers, M. T. J. Am. Chem. Soc. 1992, 114, 1083, 10941.

    Article  Google Scholar 

  13. van Koppen, P. A. M.; Kemper, P. R.; Bowers, M. T. Organometallic Ion Chemistry, Freiser, B. S., Ed.; Kluwer: Dordrecht, 1995; pp 157–196.

    Google Scholar 

  14. Armentrout, P. B.; Kickel, B. L. In Organometallic Ion Chemistry, Freiser, B. S., Ed.; Kluwer: Dordrecht, 1995; pp 1–45.

    Google Scholar 

  15. Armentrout, P. B.; Clemmer, D. E. In Energetics of Organometallic Species; Simoes, J. A. M.; Beauchamp, J. L., Eds.; Kluwer: Dordrecht, 1992; p 321.

    Google Scholar 

  16. Armentrout, P. B. ACS Symp. Ser. 1990, 428, 18.

    Article  CAS  Google Scholar 

  17. Armentrout, P. B.; Georgiadis, R. Polyhedron 1988, 7, 1573.

    Article  CAS  Google Scholar 

  18. Organometallic Ion Chemistry; Freiser, B. S., Ed.; Kluwer: Dordrecht, 1995.

    Google Scholar 

  19. Crabtree, R. H. Chem. Rev. 1985, 85, 245.

    Article  CAS  Google Scholar 

  20. Byrd, G. D.; Freiser, B. S. J. Am. Chem. Soc. 1982, 104, 5944.

    Article  CAS  Google Scholar 

  21. Huang, Y.; Wise, M. B.; Jacobson, D. B.; Freiser, B. S. Organometallics 1987, 6, 346.

    Article  CAS  Google Scholar 

  22. Buckner, S. W.; MacMahon, T. J.; Byrd, G. D.; Freiser, B. S. Inorg. Chem. 1989, 28, 3511.

    Article  CAS  Google Scholar 

  23. Gord, J. R.; Freiser, B. S.; Buckner, S. W. J. Chem. Phys. 1989, 91, 7530.

    Article  CAS  Google Scholar 

  24. Ranasinghe, Y. A.; MacMahon, T. J.; Freiser, B. S. J. Phys. Chem. 1991, 95 7721.

    Article  CAS  Google Scholar 

  25. Mandich, M. L.; Halle, L. F.; Beauchamp, J. L. J. Am. Chem. Soc. 1984, 106, 4403.

    Article  CAS  Google Scholar 

  26. Tolbert, M. A.; Mandich, M. L.; Halle, L. F.; Beauchamp, J. L. J. Am. Chem. Soc. 1986, 108, 5675.

    Article  CAS  Google Scholar 

  27. Tolbert, M. A.; Beauchamp, J. L. J. Phys. Chem. 1986, 90, 5015.

    Article  CAS  Google Scholar 

  28. Schilling, J. B.; Beauchamp, J. L. Organometallics 1988, 7, 194.

    Article  CAS  Google Scholar 

  29. Kickel, B. L.; Armentrout, P. B. J. Am. Chem. Soc. 1995, 117, 4057.

    Article  CAS  Google Scholar 

  30. Blomberg, M. R. A.; Siegbahn, P. E. M.; Sevensson, M. J. Phys. Chem. 1994, 98, 2062.

    Article  CAS  Google Scholar 

  31. Sunderlin, L. S.; Armentrout, P. B. J. Am. Chem. Soc. 1989, 111, 3845.

    Article  CAS  Google Scholar 

  32. Chen, Y.-M.; Armentrout, P. B. J. Phys. Chem. 1995, 99, 10775.

    Article  CAS  Google Scholar 

  33. Chen, Y.-M.; Armentrout, P. B. J. Am. Chem. Soc. 1995, 117, 9291.

    Article  CAS  Google Scholar 

  34. Chen, Y.-M.; Sievers, M. R.; Armentrout, P. B. Int. J. Mass Spectrom. Ion Processes 1997, 167/168, 195.

    Article  CAS  Google Scholar 

  35. Chen, Y.-M.; Armentrout, P. B. J. Phys. Chem. 1995, 99, 11424.

    Article  CAS  Google Scholar 

  36. Chen, Y.-M.; Elkind, J. L.; Armentrout, P. B. J. Phys. Chem. 1995, 99, 10438.

    Article  CAS  Google Scholar 

  37. Schilling, J. B.; Goddard, W. A., III; Beauchamp, J. L. J. Am. Chem. Soc. 1987, 109, 5565.

    Article  CAS  Google Scholar 

  38. Pettersson, L. G. M.; Bauschlicher, C. W., Jr.; Langhoff, S. R.; Partridge, H. J. Chem. Phys. 1987, 87, 481.

    Article  CAS  Google Scholar 

  39. Langhoff, S. R.; Pettersson, L. G. M.; Bauschlicher, C. W., Jr. J. Chem. Phys. 1987, 86, 268.

    Article  CAS  Google Scholar 

  40. Siegbahn, P. E. M.; Blomberg, M. R. A.; Svensson, M. Chem. Phys. Lett. 1994, 223, 35.

    Article  CAS  Google Scholar 

  41. Bauschlicher, C. W., Jr; Langhoff, S. R.; Partridge, H.; Barnes, L. A. J. Chem. Phys. 1989, 91, 2399.

    Article  CAS  Google Scholar 

  42. Siegbahn, P. E. M. J. Am. Chem. Soc. 1994, 116, 7722.

    Article  CAS  Google Scholar 

  43. Carter, E. A.; Goddard, W. A. J. Am. Chem. Soc. 1986, 108, 2180.

    Article  CAS  Google Scholar 

  44. Bauschlicher, C. W., Jr.; Partridge, H.; Sheehy, J. A.; Langhoff, S. R.; Rosi, M. J. Phys. Chem. 1992, 96, 6969.

    Article  CAS  Google Scholar 

  45. Siegbahn, P. E. M. Chem. Phys. Lett. 1993, 201, 15.

    Article  CAS  Google Scholar 

  46. Sodupe, M.; Bauschlicher, C. W., Jr. J. Phys. Chem. 1991, 95, 8640.

    Article  CAS  Google Scholar 

  47. Chen, Y.-M.; Armentrout, P. B. J. Chem. Phys. 1995, 103, 618.

    Article  CAS  Google Scholar 

  48. Ervin, K. M.; Armentrout, P. B. J. Chem. Phys. 1985, 83, 166.

    Article  CAS  Google Scholar 

  49. Schultz, R. H.; Armentrout, P. B. Int. J. Mass Spectrom. Ion Processes 1991, 107, 29.

    Article  CAS  Google Scholar 

  50. Teloy, E.; Gerlich, D. Chem. Phys. 1974, 4, 417.

    Article  CAS  Google Scholar 

  51. Gerlich, D.; Diplomarbeit, University of Freiburg, Federal Republich of Germany, 1971.

  52. Gerlich, D. In State-Selected and State-to-State Ion-Molecule Reaction Dynamics. Part 1. Experiment; Ng, C.-Y. Baer, M.; Eds.; Adv. Chem. Phys. 1992, 82, 1.

    Article  CAS  Google Scholar 

  53. Chantry, P. J. J. Chem. Phys. 1971, 55, 2746.

    Article  CAS  Google Scholar 

  54. Armentrout, P. B. In Advances in Gas Phase Ion Chemistry; Adams, N. G., Babcock, L. M., Eds.; JAI: Greenwich, 1992; Vol 1, p 83.

    Google Scholar 

  55. Shimanouchi, T. Tables of Molecular Vibrational Frequencies Consolidated, Vol I, NSRDS-NBS 39, 1972.

  56. Chen, S. S.; Wilhoit, R. C.; Zwolinski, B. J. J. Phys. Chem. Ref. Data 1975, 4, 865.

    Google Scholar 

  57. Gioumousis, G.; Stevenson, D. P. J. Chem. Phys. 1958, 29, 292.

    Google Scholar 

  58. Chen, Y.-M.; Armentrout, P. B. Work in progress.

  59. Callender, C. L.; Hackett, P. A.; Rayner, D. M. J. Opt. Soc. Am. B 1988, 5, 614.

    Article  CAS  Google Scholar 

  60. Derived using thermochemistry from Lias, S. G.; Bartmess, J. E.; Liebman, J. F.; Holmes, J. L.; Levin, R. D.; Mallard, W. G. J. Phys. Chem. Ref. Data 1988, 17, Suppl. No. 1.

  61. For a discussion of these values, see Chen, Y.-M.; Clemmer, D. E.; Armentrout, P. B. J. Chem. Phys. 1995, 95, 1228.

    Article  Google Scholar 

  62. Georgiadis, R.; Fisher, E. R.; Armentrout, P. B. J. Am. Chem. Soc. 1989, 111, 4251.

    Article  CAS  Google Scholar 

  63. Fisher, E. R.; Armentrout, P. B. J. Phys. Chem. 1990, 94, 1674.

    Article  CAS  Google Scholar 

  64. Box, G. E. P.; Hunter, W. G.; Hunter, J. S. Statistics for Experimenters; Wiley: New York, 1978.

    Google Scholar 

  65. Moore, C. E. Atomic Energy Levels; Natl. Stand. Ref. Data Ser., Natl. Bur. Stand. (NSRDS-NBS) 35, 1971; Vol II.

  66. Perry, J. K. Ph. D. Thesis, Caltech, 1994.

  67. Aristov, N.; Armentrout, P. B. J. Am. Chem. Soc. 1984, 106, 4065.

    Article  CAS  Google Scholar 

  68. Halle, L. F.; Armentrout, P. B.; Beauchamp, J. L. Organometallics 1982, 1, 963.

    Article  CAS  Google Scholar 

  69. Schultz, R. H.; Elkind, J. L.; Armentrout, P. B. J. Am. Chem. Soc. 1988, 110, 411.

    Article  CAS  Google Scholar 

  70. Schultz, R. H.; Armentrout, P. B. Organometallics 1992, 11, 828.

    Article  CAS  Google Scholar 

  71. van Koppen, P. A. M.; Bowers, M. T.; Fisher, E. R.; Armentrout, P. B. J. Am. Chem. Soc. 1994, 116, 3780.

    Article  Google Scholar 

  72. Westerberg, J.; Blomberg, M. R. A. J. Phys. Chem. A 1998, 102, 7303.

    Article  CAS  Google Scholar 

  73. Blomberg, M. R. A.; Siegbahn, P. E. M.; Svensson, M.; Wennerberg, J. Energetics of Organometallic Species; Martinho Simoes, J. A., Ed.; Kluwer: Dordrecht, 1992; pp 387–421.

    Google Scholar 

  74. Blomberg et al. have calculated energies and structures for the transition states for C-H bond activation of methane and the H-M+-CH3 intermediate formed. In their early results [16], the energies of these species with M=Ru were comparable to those with Rh. More recent calculations [57] failed to find a stable H-Ru+-CH3 species at the Hartree-Fock level (where geometries were calculated), such that no detailed results were given for Ru. Similarly, H-Rh+-CH3 does not represent a minimum on the potential energy surface at correlated levels of theory, although a stable species was located at the Hartree-Fock level.

  75. Sugar, J.; Corliss, C. J. J. Phys. Chem. Ref. Data 1985, 14, Suppl. 2.

    Google Scholar 

  76. Hanton, S. D.; Noll, R. J.; Weisshaar, J. C. J. Phys. Chem. 1990, 94, 5655.

    Article  CAS  Google Scholar 

  77. Holthausen, M. C.; Fiedler, A.; Schwarz, H.; Koch, W. J. Phys. Chem. 1996, 100, 6236.

    Article  CAS  Google Scholar 

  78. Holthausen, M. C.; Koch, W. Helv. Chim. Acta 1996, 79, 1939.

    Article  CAS  Google Scholar 

  79. Holthausen, M. C.; Koch, W. J. Am. Chem. Soc. 1996, 118, 9932.

    Article  CAS  Google Scholar 

  80. Yi, S. S.; Blomberg, M. R. A.; Siegbahn, P. E. M.; Weisshaar, J. C. J. Phys. Chem. 1998, 102, 395.

    CAS  Google Scholar 

  81. Haynes, C. L.; Fisher, E. R.; Armentrout, P. B. J. Phys. Chem. 1996, 100, 18300.

    Article  CAS  Google Scholar 

  82. Noll, R. J.; Yi, S. S.; Weisshaar, J. C. J. Phys. Chem. 1998, 102, 386.

    CAS  Google Scholar 

  83. Haynes, C. L.; Chen, Y.-M.; Armentrout, P. B. J. Phys. Chem. 1996, 100, 111.

    Article  CAS  Google Scholar 

  84. Musaev, D. G.; Morokuma, K. J. Chem. Phys. 1994, 101, 10697.

    Article  CAS  Google Scholar 

  85. Clemmer, D. E.; Aristov, N.; Armentrout, P. B. J. Phys. Chem. 1993, 97, 544.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, University of Utah, Salt Lake City, UT, USA

    P. B. Armentrout & Yu-Min Chen

Authors
  1. P. B. Armentrout
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yu-Min Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to P. B. Armentrout.

Additional information

In memory of Robert R. Squires, an outstanding contributor to ion chemistry and mass spectrometry.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Armentrout, P.B., Chen, YM. Activation of C2H6, C3H8, HC(CH3)3, and c-C3H6 by gas-phase Ru+ and the thermochemistry of Ru-ligand complexes. J Am Soc Mass Spectrom 10, 821–839 (1999). https://doi.org/10.1016/S1044-0305(99)00044-6

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1016/S1044-0305(99)00044-6

Keywords

Search

Navigation